Abstract
Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n, n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both 1H and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.
| Original language | English |
|---|---|
| Pages (from-to) | 2129-2137 |
| Number of pages | 9 |
| Journal | Inorganic Chemistry |
| Volume | 20 |
| Issue number | 7 |
| Publication status | Published - 1981 |
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ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
Uranium hexamethoxide and mixed methoxyuranium(VI) fluorides : Facile syntheses from UF6 and a nuclear magnetic resonance investigation of structure and chemical dynamics. / Cuellar, Edward A.; Marks, Tobin J.
In: Inorganic Chemistry, Vol. 20, No. 7, 1981, p. 2129-2137.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Uranium hexamethoxide and mixed methoxyuranium(VI) fluorides
T2 - Facile syntheses from UF6 and a nuclear magnetic resonance investigation of structure and chemical dynamics
AU - Cuellar, Edward A.
AU - Marks, Tobin J
PY - 1981
Y1 - 1981
N2 - Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n, n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both 1H and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.
AB - Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n, n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both 1H and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.
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M3 - Article
VL - 20
SP - 2129
EP - 2137
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 7
ER -